Hybrid Photovoltaic Cells and Related Methods

ABSTRACT

Embodiments of the present invention involve photovoltaic (PV) cells comprising a semiconducting nanorod-nanocrystal-polymer hybrid layer, as well as methods for fabricating the same. In PV cells according to this invention, the nanocrystals may serve both as the light-absorbing material and as the heterojunctions at which excited electron-hole pairs split.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of co-pending application Ser. No.13/015,316, filed Jan. 27, 2011, which is a divisional of applicationSer. No. 12/108,976, filed Apr. 24, 2008, which claims priority to andthe benefits of U.S. Provisional Application Ser. No. 60/926,103, filedon Apr. 25, 2007. Priority to each of those applications is herebyclaimed and the entirety of each of those applications is herebyincorporated by reference.

FIELD OF THE INVENTION

The present invention relates to solar cells and their fabrication, andin particular nanorod-nanocrystal-polymer hybrid solar cells

BACKGROUND

To create useful electrical current from electromagnetic radiation,photovoltaic (PV) cells must absorb incident radiation such that anelectron is promoted from the valence band to the conduction band(leaving a hole in the valence band), and must be able to separate theelectron and hole and deliver these charge carriers to their respectiveelectrodes before they recombine.

Many different strategies based on diverse materials have been employed,with varying degrees of success, to realize these basic behaviors withcommercially satisfactory efficiency. Representative devices includecrystalline inorganic solar cells (e.g., silicon, germanium, GaAs),nanocrystalline dye-sensitized solar cells, semiconductor-polymer solarcells, nanoparticle solar cells, and more recently, composite solarcells that incorporate and combine the aforementioned components fromother strategies.

1. Inorganic Photovoltaics

Silicon is by far the most commonly used material for fabricatinginorganic photovoltaics. These cells rely on the ability of silicon toabsorb light and, consequently, to generate an excited electron-holepair that is then separated at a p-n junction. The electric field set upby the p-n junction facilitates this separation because of the wayelectrons and holes move through materials: electrons move to lowerenergy levels while holes move to higher energy levels.

Creation of p-n junctions generally involves high-temperature processingin inert atmospheres to form very pure, crystalline silicon wafers,which are inflexible and expensive. Because silicon is an indirectsemiconductor, a relatively thick layer is typically needed to achieve agood level of absorption, which increases material costs further.Efficiencies for the most pure (and expensive) silicon photovoltaics areon the order of 20%; efficiencies for the cheaper amorphous siliconcells are approximately 5-10%.

Today's commercial PV systems can convert from 5% to 15% of sunlightenergy into electricity. These systems are highly reliable and generallylast 20 years or longer. The possibility of fabricating solar cells byless expensive, lower-temperature techniques is very attractive.Accordingly, nanocrystalline dye-sensitized solar cells (DSSCs),semiconductorpolymer solar cells and nanoparticle solar cells haveenjoyed widespread interest.

2. Polymer Photovoltaics

Semiconducting polymers can be used to make organic photovoltaics. Theproperties of these polymers can be tuned by functionalization of theconstituent monomers. As such, a wide range of polymers with suitablebandgaps, absorption characteristics and physical properties isavailable. In order to achieve separation of the electron-hole pair,organic photovoltaics rely on donor-acceptor heterojunctions. Inpolymers, the excited-state electron and hole are bound together, andtravel together, as a quasi-particle called an exciton. They remaintogether until they encounter a heterojunction, which separates them.Unfortunately, excitons are very shortlived and can only travel about 10nm before recombining. Hence, any photon absorbed more than thisdiffusion length away from a heterojunction will be wasted. Chargemobilities for polymers are typically low (0.5-0.1 cm² V⁻¹ s⁻¹) comparedto silicon, which is much higher (1500 cm² V⁻¹ S⁻¹). Currentstate-of-the-art polymer photovoltaic cells have efficiencies of 1-2%.Although such efficiencies are low, these materials hold promise forlow-cost, flexible solar cells.

3. Nanoparticle Photovoltaics

Inorganic nanoparticles (or nanocrystals) have been used to preparecolloidal, thin-film PV cells that show some of the advantages ofpolymer photovoltaics while maintaining many of the advantages ofinorganic photovoltaics. For example, such cells can contain a bi-layerstructure comprising a layer of donor and a layer of acceptornanoparticles, wherein the two layers exhibit little intermixing, andboth contribute to the measured photocurrent. The strong photoconductiveeffect exhibited by these devices suggests that these materials have alarge number of trapped carriers and are better described by adonor-acceptor molecular model than by a p-n band model. Increasedbandgap energy compared to that of the bulk semiconductors minimizes thenumber of carriers available, and spatial separation of the donor andacceptor particles in different phases traps the excitons so that theymust split at the donor-acceptor heterojunction. There is noband-bending, so splitting of the exciton is more difficult.

It should be stressed that simply blending the donor and acceptornanoparticles together will not create a film that produces aphotovoltage. The lack of selectivity at the electrode towards oneparticle or another means that the electrodes can make contact with boththe donor and acceptor species. These species may take the form ofnanorods rather than nanospheres because nanorods with high aspectratios help to disperse the carriers. Quick transfer of the excitonalong the length of the nanorods improves the chance of splitting theexciton at the donor-acceptor heterojunction.

Solution processing of, for example, CdSe rods can achieve a sizedistribution of 5% in diameter and 10% in length with an aspect ratio of20 and a length of 100 nm. The substantial control available throughsolution processing allows for optimization of the cell by variation ofnanorod length and bandgap energy.

4. Polymer-Nanocrystal Composite Photovoltaics

The combination of nanomaterials and polymer films has been shown togive good power conversion efficiencies while affording low-temperaturesolution processes for fabrication. In one approach, nanomaterials areused to conduct charges while the polymer is used as the absorbingmaterial, or alternatively, the nanomaterial serves as a chromophore,i.e., the light absorber, and the semiconductor polymer is employed as ahole conductor. In the former case, a wide-bandgap semiconductor (e.g.,TiO₂) receives the excited electron from the conduction band of thechromophoric polymer semiconductor; and in the latter case,light-absorbing semiconductor nanocrystals absorb photons and transferthe resulting negative charge to the transparent primary electrode,while the semiconducting polymer transfers the holes to the counterelectrode. In both types of cell, a heterojunction between thenanocrystal and the polymer separates the exciton created in thenanocrystal or polymer. The electron is transferred to the conductionband of the nanocrystal and the hole stays in the valence band of thepolymer, or the electron stays in the conduction band of thenanocrystal, and the hole is transferred to the valence band of thepolymer.

4.1 Wide-Bandgap Nanocrystal/Light-Absorbing Polymer

The active layer in a polymer-nanocrystal cell has two components: alight absorber and a nanoparticulate electron carrier. Typically, thelight absorber is a p-type polymeric conductor, e.g., poly(phenylenevinylene) or poly(3-hexylthiophene), and the nanoparticulate electroncarrier is a wide-bandgap semiconductor such as ZnO or TiO₂. In thisconfiguration, the polymer serves to absorb light, to transfer electronsto the electron acceptor/carrier, and to carry holes to the primaryelectrode. The electron acceptor accepts electrons and transfers theelectrons to the metal back contact.

The morphology of the phase separation is crucial. For example, abi-layer structure in which each layer has only one component results ina cell with poor performance. The reason is that the lifetime of theexcited state of the light-absorbing polymer is generally shorter thanthe transfer rate of the exciton to the interface, and, consequently,the majority of the excitons formed in the bulk of the polymer neverreach the interface separating electrons and holes, resulting in loss ofphoto current. Morphologies in which a bulk heterojunction is formedtend to show greater efficiencies. If the absorber and electron acceptorare in intimate contact throughout the entire active layer, the shorterexciton path length will result in increased electron transfer andhigher efficiencies. The best efficiencies obtained from cells of thisconfiguration are around 2%.

This technology shows promise, but there are obstacles to overcome. Oneproblem is incomplete absorption of the incident radiation. Thepolymer—which absorbs light very strongly and is referred to as apolymeric dye—has a large extinction coefficient (>100,000 M⁻¹ cm⁻¹),but due to low exciton migration rates, the films must generally bethinner than 100 nm, which contributes significantly to incompleteabsorption. This effect can be combated by means of an interdigitatedarray structure of donor and acceptor species.

4.2 Wide-Bandgap Nanocrystal/Light-Absorbing Nanocrystals/Hole TransferPolymer

A problem associated with the light-absorbing polymer strategy isunderutilization of available solar energy due to the narrow absorptionbandwidth of typical polymers. Approximately 40% of the light (fromabout 600 nm out into the near IR) can be wasted. An alternativeconfiguration is to utilize nanocrystals as light absorbers and electroncarriers, and employ the polymer as a light absorber and a hole carrier.CdSe nanorod and tetrapod/polymer systems have demonstratedpower-conversion efficiencies of up to 1.7%. These systems have theadvantage that the absorption of the nanocrystal can be tuned via thesize of the nanocrystal, and systems that absorb essentially all of theincoming radiation can therefore be fabricated.

Unfortunately, it is difficult to disperse inorganic nanocrystals into asolution of monomers. The two phases tend to agglomerate and minimizethe electrical contact essential to form the heterojunction whichenables charge separation. Dispersion of nanocrystals in polymer phasesis an area of great interest.

Typically, the strategy employed for dispersing the nanocrystals is tofunctionalize the nanocrystal with a capping agent that has an organictail, which enhances solubility in the solvent in which thepolymerization is carried out. Capping agents for this purpose typicallyhave a head-group with a strong affinity for the nanocrystal; amine,carboxylate, phosphine, thiol, phosphine oxide and phosphonic acid, forexample, all bind strongly. The organic tail of the capping agent shouldbe compatible with solvents in which the polymer is soluble. Longhydrocarbon chains typically provide high solubility but arenon-conducting; accordingly, it is necessary to balance optimumsolubility against conductivity.

The most popular polymers used for composite studies are PDFC, P3Ht andMEH-PPV (where PDFC refers to-{poly[9,9-dohexylfluorenyl-2,7-diyl)-alt-co-(9-ethyl-3,6-carbazole)]}-,P3Htrefers to poly(3-hexylthiophene), and MEH-PPV refers topoly(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene)). Each ofthese polymers has sites for functionalization, allowing themanipulation of the valence/conduction band energies to achieve optimalconditions for charge transfer to and from the nanocrystals. It has beensuggested that the capping agent may also serve as the organic acceptorphase; for example, P3HT functionalized with phosphonic acid groups hasbeen shown to isolate CdSe nanocrystals.

5. Dye-Sensitized Solar Cells

DSSCs incorporate a substrate which has been coated with a transparentconducting oxide (which serves as the primary electrode). The counterelectrode may also be coated with a transparent conducting oxide, butmay also be a non-corrosive metal, such as titanium coated with a verythin layer of platinum. A porous layer of a wide-bandgap semiconductor(such as TiO₂) is deposited on the conductive surface of the primaryelectrode. This porous layer is then coated with a dye having a strongabsorption in the visible region of the spectrum. To be optimallyeffective, the dye concentration should be limited to a monolayer of dyemolecules. Because of this, a huge surface area is necessary toaccommodate enough dye to absorb all of the incoming light. Therefore,nanocrystals (e.g., TiO₂) are used to make the highly porous films.Electrolyte containing a redox couple (typically I⁻/I₃ ⁻) is absorbedinto the titania layer. To complete the cell, the substrate bearing theprimary electrode and the sensitized titania layer is brought intoface-to-face contact with the counter electrode.

Typical dyes are inorganic-ruthenium-based, although organic dyes arereceiving increased interest. The dye absorbs visible light, and theexcited state injects an electron into the TiO₂ conduction band. Beforeback electron transfer can occur, the oxidized dye is reduced by a redoxactive species in solution (typically I⁻/I₃ ⁻), regenerating the dye.The oxidized redox active species diffuses to the counter electrode,where it is reduced, finishing the cycle and completing the circuit.Work can be done by passing the injected electron through an externalload before allowing it to reduce the oxidized redox active species atthe counter electrode.

Inexpensive DSSC devices, which exhibit up to 10% energy conversionefficiency, can be fabricated. There are many issues to be addressedwith this technology to improve performance and stability, includingreplacing the best performing liquid electrolytes with solid state orhigher-boiling electrolytes; improving spectral overlap; using a redoxmediator with a lower redox potential; and lowering recombination lossesdue to poor electron conduction through the nanoparticle TiO₂ layer.

6. Hybrid Cells

Hybrid cells combine dye-sensitized titania, coated and sintered onto atransparent semiconducting oxide, with a p-type polymer that carrieselectrons to the oxidized dye. Since just one polymer replaces themulti-component electrolyte, these cells can be fabricated convenientlyand reproducibly. Ruthenium dye-sensitized, nanorod-based DSSCs tend toexhibit low efficiency, however, because the lower surface area does notaccommodate enough dye to absorb all of the incident light. The mostefficient dyes found so far only have extinction

coefficients on the order of 20,000 M⁻¹ cm⁻¹, and therefore a largesurface area is needed to bind enough dye to get maximal absorbance.

SUMMARY OF THE INVENTION

Aspects of the present invention provide a photovoltaic (PV) cellcomprising a semiconducting nanorod-nanocrystal-polymer hybrid layer, aswell as methods for fabricating the same. In PV cells according to thisinvention, the nanocrystals serve both as the light-absorbing materialand as the heterojunctions at which the excited electron-hole pairs(i.e., excitons) split. The nanorods function as electron carriers andare electrically connected to the anode of the cell, and the polymeracts as the hole carrier and is electrically connected to the cathode ofthe cell.

One of the advantages of the invention lies in the use of smallparticles, the nanocrystals, as both light absorber and heterojunction.The resulting spatio-temporal proximity of exciton generation andsplitting entails a significant reduction in recombination losses,compared, for example, with those of conventional polymer PV cells, andconsequently in higher conversion efficiencies of photons intoelectricity. Embodiments of the invention offer the additionaladvantages of mechanical flexibility and low cost manufacturingprocesses.

Accordingly, in a first aspect, the invention provides a photovoltaiccell containing two electrodes and, in between these electrodes, aplurality of aligned semiconducting nanorods surrounded by and bound toa plurality of photoresponsive nanocrystals, and a semiconductor polymersurrounding the nanorods and bound to the nanocrystals. The nanocrystalsact as heterojunctions channeling electrons into the nanorods and holesinto the polymer, or vice versa. The nanorods are electrically connectedto the first electrode, and electrically insulated from the secondelectrode by a thin layer of polymer bound to the second electrode. Invarious embodiments, the polymer is a hole-transfer polymer, andconsequently, the nanocrystals channel holes into the polymer andelectrons into the nanorods. In various embodiments, the nanocrystalsare bound to the nanorods by a bifunctional capping agent, which can,for example, be mercaptoacetic acid. For example, the nanorods may begrown on the first electrode, and the other electrode can later bedeposited on the nanorod-nanocrystal-polymer layer in a manner ensuringinsulation of the nanorods from the second electrode.

Advantageous nanorods have aspect ratios (i.e., ratios of the longestdimension to the shortest dimension of the particle) of at least 3, andtheir shortest dimension is not greater than 100 nm. Preferred nanorodsare single-crystalline. Suitable nanorod materials according to theinvention include, but are not limited to, wide bandgap semiconductorssuch as, for example, ZnO, SnO, and TiO₂, whereby ZnO is the preferredmaterial.

Suitable nanocrystals according to the invention include semiconducting,monocrystalline or polycrystalline nanoparticles of diameter not greaterthan 20 nm, which may (but need not) be generally spherical in shape.Suitable nanocrystal materials include, but are not limited to CuInSe₂,CuInS₂, CuIn_(1-x)Ga_(x)Se₂ (where 0≦x≦1), GaAs, InAs, InP, PbS, PbSe,PbTe, GaSb, InSb, CdTe and CdSe. Nanocrystals with extinctioncoefficients of at least 100,000 M⁻¹ cm⁻¹ are preferred. In variousembodiments, the largest spatial dimension of the nanocrystals is nogreater than the average diffusion distance of the excitons created inthe nanocrystal upon absorption of light.

Suitable polymer materials include, but are not limited to,poly(3-hexylthiophene), polyphenylenevinylene (PPV) and its derivatives,and polyfluorene (PFO) and its derivatives. In various embodiments, thepolymer is bound to the nanocrystals but not to the nanorods.

In a second aspect, the invention provides a method of fabricating asemiconductor structure with heterojunctions; the structure can be usedin a photovoltaic cell. Embodiments of the method involve providing aplurality of nanorods and a plurality of photoresponsive nanocrystalscapped with a first capping agent; exposing the nanorods or thenanocrystals to a second, bifunctional capping agent; then combining thenanocrystals with the nanorods so that the nanocrystals bind to thenanorods via the bifunctional capping agent; combining the boundnanorods and nanocrystals with a functionalized monomer which has abinding group with (i) stronger affinity for the nanocrystals than thefirst capping agent and (ii) weaker affinity for the nanorods than thebifunctional capping agent, so that the monomer preferentially displacesthe first capping agent and binds to the nanocrystals; and polymerizingthe monomer. The bifunctional capping agent can first bind to thenanorods, and then bind to the nanocrystals, replacing some of the firstcapping agent. Alternatively, the bifunctional capping agent can firstbind to the nanocrystals (replacing some of the first capping agent),and then bind with its free ends to the nanorods. In variousembodiments, the first capping agent contains a thiol, selenol, amine,phosphine, phosphine oxide, and/or aromatic heterocycle functionality. Anon-limiting example of a suitable capping agent is octanethiol.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing discussion will be understood more readily from thefollowing detailed description of the invention when taken inconjunction with the accompanying drawings.

FIG. 1A schematically depicts an embodiment of ananorod-nanocrystal-polymer hybrid solar cell according to theinvention.

FIG. 1B is an enlarged schematic view of the three major components ofthe hybrid semiconductor layer of FIG. 1A, and of theirinterconnections.

FIG. 2A is a flow diagram detailing a method of fabricating thestructure depicted in FIG. 1A according to one embodiment.

FIG. 2B is a flow diagram detailing a method of fabricating thestructure depicted in FIG. 1A according to an alternative embodiment.

FIG. 3 illustrates at a microscopic level some of the steps of themethod shown in FIG. 2 and the resulting products.

DETAILED DESCRIPTION OF THE INVENTION 1. Nanorod-Nanocrystal-PolymerHybrid Structure

In polymer-based photovoltaics, excitons travel on average of the orderof 10 nm before recombining; accordingly, there is a need to separatethe excitons, i.e., to have them encounter a heterojunction as soon aspossible. This need is met in embodiments of the present invention, inwhich nanocrystals (quantum dots) serve as a bridge between ahole-transfer polymer and a wide-bandgap semiconductor electronacceptor, thus constituting the heterojunction, and serve simultaneouslyas the light absorber, i.e., the place where the excitons are created.The diameter of a nanocrystal according to the invention isapproximately equal to, or smaller than, the diffusion distance of anexciton. As a result, an exciton generated in the nanocrystal willgenerally encounter the interface of the nanocrystal with the electronacceptor or the hole-transfer polymer within its average diffusiondistance, regardless of the direction in which it migrates.Consequently, the exciton splits very efficiently, and recombinationwithin the nanocrystal occurs infrequently. The electron enters into thewide-bandgap semiconductor, and the hole enters into the polymer.

The structure of a PV cell 100 according to the invention is illustratedin FIG. 1A. In between two electrodes, an anode 101 and a cathode 103, aplurality of aligned wide-bandgap semiconductor nanorods 106, whichconstitute the electron acceptor, is arranged. As shown in the detail ofFIG. 1A, the nanorods 106 are each surrounded by photosensitivenanocrystals 109.

The sensitized nanorods, in turn, are surrounded by the hole-transferpolymer 112, which fills the remaining space between the electrodes 101,103. The polymer 112 also forms a thin layer underneath the cathode 103,which electrically isolates the cathode 103 from the sensitized nanorods106.

FIG. 1B shows how these three components are interconnected in preferredembodiments of the invention. The nanocrystals 109 are bound to thenanorods 106 by means of a bifunctional binding molecule 115. In variousembodiments, the bifunctional capping agent 115 has thiol andcarboxylate moieties. The thiol groups bind preferentially to thenanocrystals 109, and the carboxylate groups bind preferentially to the(metal oxide) nanorods 106. The intervening chain should be short enoughso that charge transfer from nanocrystal 109 to nanorod 106 is notimpeded. A representative bifunctional capping agent 115 ismercaptoacetic acid. The holetransfer polymer 112 is directly bound tothe nanocrystals 109, but preferably not to the nanorods 106.

A representative, non-limiting example of a system of nanorods,bifunctional molecules, nanocrystals, and polymers comprises ZnOnanorods capped with mercaptoacetic acid, CuInSe₂ quantum dots, andpoly(3-hexylthiophene).

1.1 Nanocrystals 109

The semiconductor material used for nanocrystals in a particularapplication depends on the suitability of valence and conduction bandenergy levels. The conduction band should be of sufficient energy to beable to inject electrons efficiently into the nanorods, while thevalence band should be of sufficiently low energy to inject holes intothe polymer valence band. The latter constraint is generallystraightforward to satisfy, as suitable polymers having a higher energyvalence band than the nanocrystal can readily be identified. Subject tothe above constraints, the bandgap of the nanocrystal should be smallenough to allow for a large portion of the solar spectrum to beabsorbed. Suitable nanocrystal materials include materials based oncopper-indium-diselenide and variants thereof, for example, CuInS₂,CuInSe₂, or CuIn_(1-x)Ga_(x)Se₂ (wherein 0₂≦x≦1), as well as CdSe, GaAs,InAs, and InP.

Nanocrystals can be synthesized using techniques described, for example,in U.S. Pat. No. 6,379,635 and co-pending U.S. patent application Ser.Nos. 11/579,050 and 11/588,880, the entire contents of which are herebyincorporated by reference.

A method for producing CIGS nanocrystals of any desirable stoichiometryemploying a selenol compound is disclosed in U.S. ProvisionalApplication Ser. No. 60/991,510, the entire content of which is herebyincorporated by reference. Embodiments of the method involve dispersingat least a first portion of a nanocrystal precursor composition(comprising sources of at least one of Al, Ga, and/or In, and at leastone of Cu, Ag, Zn, and/or Cd) in a solvent (e.g., along-chainhydrocarbon solvent); heating the solvent to a first temperature for anappropriate length of time; adding a selenol compound to the solvent andheating the solvent; adding a second portion of the nanocrystalprecursor composition to the reaction mixture; heating the mixture to asecond temperature higher than the first temperature over an appropriatelength of time; and maintaining the temperature for up to 10 hours. Oncethe particles have been formed, the surface atoms of the particles willtypically be coordinated to a capping agent, which can comprise theselenol compound employed in the method. If a volatile selenol compoundis used, this capping agent can be driven off with heating to yield‘naked’ nanocrystals amenable to capping with other coordinating ligandsand further processing. Examples 1 and 2 provide further detailsregarding the implementation of this method:

Example 1

Cu(I) acetate (1 mmol) and In(III) acetate (1 mmol) are added to a cleanand dry RB-flask. Octadecene ODE (5 mL) is added the reaction mixtureheated at 100° C. under vacuum for 30 mins. The flask is back-filledwith nitrogen and the temperature raised to 140° C. I-octane selenol isinjected and the temperature falls to 120° C. The resulting orangesuspension is heated with stirring and a transparent orange/red solutionis obtained when the temperature has reached 140° C. This temperature ismaintained for 30 minutes, then 1M tri-octyl-phoshine selenide TOPSe (2mL, 2 mmol) is added dropwise and the solution heated at 160° C. The PLis monitored until it reaches the desired wavelength, after which it iscooled and the resulting oil washed with methanol/acetone (2:1) 4-5times and finally isolated by precipitation with acetone.

Example 2 Large Scale Production

A stock solution of TOPSe was prepared by dissolving Se powder (10.9,138 mmol) in TOP (60 mL) under nitrogen. To dry, degassed ODE was addedCu(I) acetate (7.89 g, 64.4 mmol) and In(III) acetate (20.0 g, 68.5mmol). The reaction vessel was evacuated and heated at 140° C. for 10min, backfilled with N₂ and cooled to room temp. I-Octane selenol (200mL) was added to produce a bright orange suspension. The temperature ofthe flask was raised to 140° C. and acetic acid distilled from thereaction at 120° C. On reaching 140° C. the TOPSe solution was addeddropwise over the course of 1 hour. After 3 hours the temperature wasraised to 160° C. The progress of the reaction was monitored by takingaliquots from the reaction periodically and measuring the UV/Visible andphotoluminescence spectra. After 7 hours the reaction was cooled to roomtemperature and the resulting black oil washed with methanol. Methanolwashing was continued until it was possible to precipitate a fine blackmaterial from the oil by addition of acetone. The black precipitate wasisolated by centrifugation, washed with acetone and dried under vacuum.Yield: 31.97 g.

For the purpose of optimizing the composition, size, and charge of thenanocrystals, they can be characterized by conventional techniques,including, but not limited to, XRD, UV/Vis/Near-IR spectrometry, SEM,TEM, EDAX, photoluminescence spectrometry, and elemental analysis.

Some embodiments of the invention utilize nanocrystals with extinctioncoefficients of at least 100,000 M⁻¹ cm⁻¹. At such high absorptivities,fewer nanocrystals are needed to achieve the same overall absorption.Consequently, embodiments of this invention based on these nanocrystalscan benefit from increased absorption without incurring losses inefficiency due to enhanced recombination.

1.2 Nanorods 106

Nanorods can be produced by direct chemical synthesis, utilizing asuitable combination of ligands such as trioctylphosphine oxide (TOPO)and various phosphonic acids, e.g., octadecylphosphonic acid, for shapecontrol. Moreover, different types of metal oxides can be grown inordered nanorod arrays, using techniques such as, for example,electrochemical etching of metal foil, or substrate seeding followed bynanorod growth, in a chemical bath, in a direction perpendicular to thesubstrate. See, e.g., D. C. Olson et al., J. Phys. Chem. C, 2007, 111,16640-5 16645; and J. Yang et al., Crystal Growth & Design, 2007,12/2562, the disclosures of which are hereby incorporated by referencein their entireties.

In preferred embodiments of the invention, the nanorods have high aspectratios exceeding 3, and are up to 200 nm long. A preferred nanorodmaterial is ZnO. Other materials that might be suitable include SnO,TiO₂, and other metal oxides.

As mentioned previously, the small size of the nanocrystals greatlyreduces recombination within the particle. In order to further reducerecombination losses, preferred embodiments of the invention utilizesingle-crystal nanorods. While in nanoporous particlebased films, suchas those employed in DSSC cells, electrons percolate slowly through thefilm, enabling recombination with the electrolyte to take place,electron transfer through single-crystal nanorods is very fast, whichlimits the recombination of electrons from the nanorods with holes inthe nanocrystals or the polymer.

In preferred embodiments and as discussed in greater detail below, thenanorods are coated with a layer of a bifunctional capping agent, whichbinds the quantum dots closely to the nanorods, thereby preventing thesemiconductor polymer from coming into the proximity of the nanorod,which diminishes nanorod-polymer recombination losses even further.

1.3 Polymer 112

Polymer 112 should have a valence band energy that allows holes toefficiently transfer from the nanocrystal valence band to the polymervalence band. Suitable polymers include poly(3-hexylthiophene),polyphenylenevinylene (PPV) and its derivatives, and polyfluorene (PFO)and its derivatives. These polymers are efficient hole-transfer polymersdue to the high hole mobility in organic materials.

2. Method for Fabricating a Nanorod-Nanoparticle-Polymer HybridStructure

Hybrid semiconductor structures according to the invention can befabricated using lowcost deposition technologies, such as printing, dipcoating, or chemical bath deposition. An important considerationregarding fabrication is control over where the various pieces bindtogether. For example, binding of the polymer to the nanorod would mostlikely result in substantial losses in efficiency due to recombination.In preferred embodiments, the nanocrystals are bound to both thenanorods and to the semiconducting polymer to promote optimalperformance as a heterojunction, and the polymer is not directly boundto the nanorods. This structure can be achieved with suitable cappingagents in appropriate processing steps.

FIGS. 2A and 2B illustrate representative process sequences 200A and200B implementing embodiments of the present invention. Some steps ofthese sequences, and the structures they result in, are furtherillustrated in FIG. 3 at a microscopic level. In a first step 202,nanorods are grown on an anodic substrate, e.g., by printing seeds onthe substrate and then growing the nanorods perpendicularly to thesubstrate via a chemical bath. In this structure, the nanorods areinherently in electrical contact with the substrate. In subsequentsteps, the nanocrystals and monomers are introduced to the resultingfilm of aligned nanorods.

In step 204, nanocrystals capped with a (first) capping agent whichcontains functionalities that bind weakly to the nanocrystals areprovided. Suitable functionalities include thiol, selenol, amine,phosphine, phosphine oxide, and aromatic heterocycles. Typically, thenanocrystals are dissolved in a non-polar organic solvent. The cappingagent serves to control binding of the nanocrystals to the nanorods andthe polymer; the bond is reversible and the capping agent can later beexchanged for other ligands. Examples of capping agents suitable for usewith CuInSe₂ nanocrystals are octanethiol or pyridine.

In steps 206, 208, the nanorods are coated by the nanocrystals, wherebythe bond between nanorods and nanocrystals is established via thebifunctional capping agent 115 (e.g., mercaptoacetic acid), which hasstrong binding groups for both the nanorods and the nanocrystals. Thiscan be accomplished in different ways. In some embodiments, asillustrated in FIG. 2A and FIG. 3, the nanorods are capped with thebifunctional capping agent (step 206A), for example, by dipping thesubstrate with the nanorods into a solution of the bifunctional cappingagent. For example, the capping agent may be bound to the nanorods via acarboxylate functionality. The capped nanocrystals 302 are thenintroduced to the film of capped nanorods 300 (step 208A), for example,by dipping the rinsed substrate with nanorods 300 into the nanocrystalsolution(s). At this stage, a fraction of the weak capping agent of thenanocrystals is replaced by the stronger binding groups of thebifunctional capping agent, e.g., the thiol functionality ofmercaptoacetic acid, which results in nanocrystal-sensitized nanorods304.

In alternative embodiments, as illustrated in FIG. 2B, a solution of thecapped nanocrystals in a non-polar organic solvent is added to asolution of the bifunctional capping agent in a polar organic solventwhich is not miscible with the non-polar solvent, and the solution isshaken to ensure good mixing (step 206B). The nanocrystals undergoligand 10 exchange and transfer from a non-polar organic phase to apolar organic phase. Subsequently, the substrate with the alignednanorods on the surface is dipped into the nanocrystal solution orotherwise exposed to the nanocrystals (step 208B), whereby the nanorodsbind the nanocrystals via a carboxylic acid functionality of the cappingagent. These embodiment likewise result in nanocrystal-sensitizednanorods 304.

The monomers are functionalized (step 210) with a binding group that hasa stronger affinity for the nanocrystals than the (first) nanocrystalcapping agent, but a weaker affinity for the nanorods than thebifunctional capping agent. Moreover, the affinity of the binding groupat the monomer for the nanocrystal is preferably weaker than theaffinity of the bifunctional capping agent for the nanocrystal. Themonomer functionality should not interfere with the polymerizationreaction. Binding groups with suitable differential binding affinitiesare straightforwardly identified by those of skill in the art withoutundue experimentation based on the identities of the capping agents andtheir substituents (e.g., whether they are unidentate or multidentate,or on the presence of electron withdrawing groups, etc.) and the size ofthe nanocrystal. The functionalized monomers are then combined with thenanocrystal-sensitized nanorods (step 212), where they bind to thenanocrystals (but not the nanorods), preferentially replacing the weakcapping agent on the nanocrystal, but leaving the nanorod-nanocrystalbond intact, resulting in structure 306. A subsequent polymerizationstep 214 results in the nanorodnanocrystal-polymer semiconductorstructure 308.

Finally, a metal cathode (e.g., Al) can be deposited on the structure(step 216), for example, by sputtering or metal evaporation, so that thenanorods form an array of aligned rods deposited between two opposingelectrodes. The polymer layer below the cathode should be sufficientlythick to electrically isolate the cathode from the nanorods.

Although the present invention has been described with reference tospecific details, it is not intended that such details should beregarded as limitations upon the scope of the invention, except as andto the extent that they are included in the accompanying claims.

What is claimed is:
 1. A photovoltaic cell comprising: a. first andsecond electrodes; a. b. a plurality of semiconducting nanorods disposedbetween the electrodes, wherein the nanorods are electrically connectedto the first electrode and electrically insulated from the second; c. aplurality of photoresponsive nanocrystals bound to the nanorods via abifunctional capping agent; and d. a semiconductor polymer bound to thenanocrystals and bound the second electrode but not bound to thenanorods.
 2. The cell of claim 1 wherein (i) the polymer is ahole-transfer polymer, (ii) the first charge carrier is electrons, and(iii) the second charge carrier is holes.
 3. The cell of claim 2 whereinthe polymer is poly(3-hexylthiophene), polyphenylenevinylene or aderivative thereof, or polyfluorene or a derivative thereof.
 4. The cellof claim 1 wherein the nanorods are wide-bandgap semiconductors.
 5. Thecell of claim 4 wherein the nanorods comprise at least one of ZnO, SnO,and/or TiO₂.
 6. The cell of claim 1 wherein the nanorods aresingle-crystal nanorods.
 7. The cell of claim 1 wherein the nanorodshave an aspect ratio of at least
 3. 8. The cell of claim 1 wherein thecapping agent is mercaptoacetic acid.
 9. The cell of claim 1 whereinabsorption of light by a nanocrystal results in production of anexciton, the nanocrystal having a largest spatial dimension no greaterthan an average diffusion distance of the exciton.
 10. The cell of claim1 wherein the nanocrystals comprise at least one of CuInSe₂, CuInS₂,CuIn_(1-x)Ga_(x)Se₂, GaAs, InAs, InP, PbS, PbSe, PbTe, GaSb, InSb, CdTeand CdSe, wherein 0≦x≦1.
 11. The cell of claim 1 wherein thenanocrystals have extinction coefficients of at least 100,000 M⁻¹cm⁻¹.